Dispersion of Fluorosilicones and Fluorine- and Silicon-Containing Surface Treatment Agent

ABSTRACT

A fluorosilicone reaction product of a mercapto or vinyl functional organopolysiloxane and a fluorine-containing monomer, and methods of preparing the fluorosilicone are disclosed. The fluorosilicone products are suitable for application to substrates such as textiles, particularly fabrics, to impart oil repellent properties to the textile. The fluorosilicone reaction product is prepared from (A) a fluorine-containing monomer of the formula CH 2 ═C(X)COOYRf, and (B) a mercapto or vinyl functional organopolysiloxane.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application claims benefit under 35 U.S.C. §119(e) of U.S.Provisional Application No. 61/040,734 filed Mar. 31, 2008, incorporatedherein by reference in its entirety.

TECHNICAL FIELD

This invention relates to a dispersion of fluorosilicone reactionproduct of a mercapto, vinyl or (meth)acrylamide, functionalorganopolysiloxane and a fluorine-containing monomer, and methods ofpreparing the fluorosilicone. The dispersion of fluorosilicone productsare suitable for application to substrates such as textiles,particularly fabrics, to impart oil repellent properties (oleophobicity)to the textile.

The dispersion of fluorosilicone reaction product (that is, a fluorine-and silicon-containing polymer) is useful for a surface treatment agentimparting excellent water repellency, oil repellency, soil resistance,and feeling to a substrate such as a textile.

BACKGROUND ARTS

Fluorocarbon polymers are extensively used in the textile industry toimpart oleophobicity/oil repellency to a fabric. For example, U.S. Pat.No. 5,247,008 describes finishing agents for textiles, leather, paperand mineral substrates which are aqueous dispersions of a copolymer of aperfluoroalkyl acrylate or methacrylate, an alkyl acrylate ormethacrylate and an aminoalkyl acrylate or methacrylate.

U.S. Pat. No. 5,068,295 describes a water and oil repellent comprising acopolymer of a perfluoroalkyl acrylate or methacrylate, apolyorganosiloxane containing a vinyl group and a vinyl monomercontaining an isocyanate or blocked isocyanate group.

U.S. Pat. No. 6,582,620 and U.S. Pat. No. 5,883,185 describe a treatingcomposition for textiles to render them water and oil repellent obtainedby cohydrolysis and condensation of (A) a fluorinated alkyl-bearingalkoxysilane, (B) an amino-bearing alkoxysilane, and (C) analkoxysilyl-bearing polyorganosiloxane.

U.S. Pat. No. 5,536,304 describes application of a blend of a succinicanhydride-terminated polydimethylsiloxane and a poly(fluoroalkylmethacrylate) to cotton to give a fabric with oil repellency.

U.S. Pat. No. 6,472,019 describes treating a textile with a water- andoil-repellent agent comprising a fluorine-containing polymer and asulphated fatty acid compound and WO 2004/069935 and WO 2004/069955describe a fluorine containing polymer delivered as an aqueousdispersion for textile treatment.

One of the major disadvantages of topical finishes prepared withfluorocarbon polymers is that they impart a harsh feel to the fabricsurface. There is a need for textile treatment agents which impartoleophobicity and oil repellency to fabrics without imparting a harshfeel to the fabric surface, and preferably whilst at the same timeimparting an improvement in feel compared to untreated fabric.

Hitherto, in order to give both water- and oil-repellency and softnessto a substrate such as a textile, a water- and oil-repellent compositioncomprising a perfluoroalkyl group giving water- and oil-repellency and asilicone compound giving softness has been widely used. Please see, forexample, JP-A-58-42682, JP-A-60-190408, JP-A-63-075082, JP-A-09-143877,and U.S. Pat. No. 4,070,152.

There is, for example, a method of using a copolymer of afluorine-containing acrylate monomer and a silicone acrylate monomer forthe same purpose (for example, JP-A-02-214791 and JP-A-03-231986). Thismethod, however, has the problem that the water- and oil-repellency isdecreased.

By the way, the fluoroacrylate polymer used as the conventional surfacetreatment agent needs at least 8 carbon atoms in the fluoroalkyl groupso as to give sufficient water- and oil-repellency. Since saidfluoroacrylate polymer has high hydrophobicity, in the case of emulsionpolymerization, there are necessity that the amount of the usedemulsifier is large, the problem that the type of the emulsifier islimited, and the necessity that an aid solvent should be used due topoor compatibility with another fluorine-free monomer.

Various recent research results indicate that in view of the practicaltreatment of fibers with the surface treatment agent (particularly thewater- and oil-repellent agent), the important surface property is not astatic contact angle, but is a dynamic contact angle, particularly areversing contact angle. That is, the advancing contact angle of wateris not dependent on the carbon number of the fluoroalkyl side chain, butthe reversing contact angle of water in the case of carbon number of atmost 7 is remarkably low than that in the case of carbon number of atleast 8. In correspondence to this, an X ray analysis shows that theside chain crystallizes when the carbon number of side chain is at least7. It is known that the actual water repellency has relationship withthe crystallization of the side chain and that mobility of the surfacetreatment agent molecules is an important factor for expression of theactual performances (for example, MAEKAWA takashige, FINE CHEMICAL, Vol.23, No. 6, page 12 (1994)). Accordingly, it is believed that theacrylate polymer having low carbon number of fluoroalkyl group in theside chain which is at most 7 (particularly at most 6) has lowcrystallinity so that the polymer cannot satisfy the actual performances(particularly water repellency).

Hitherto, it is known that the fluorine-containing acrylate polymerhaving an alpha position substituted with fluorine, chlorine or the likehas good adhesion to a substrate, forms a film having a large strength,and imparts good water- and oil-repellency (JP-A-63-90588, JP-A-63-99285and JP-A-01-315471). These publications also show that the carbon numberof the fluoroalkyl group used in working examples is at least 8, andthese publications do not think the use of the acrylate monomer havingfluoroalkyl group having at most 6 carbon atoms.

It is proposed to use the fluorine-containing acrylate polymer which hasthe fluoroalkyl group having at most 4 carbon atoms and in which thealpha position is substituted with fluorine, chlorine or the like (forexample, WO2004-096939). Since the polymer film, however, is strong, thefeeling of the treated textile is problematically deteriorated.

A method of adding a silicone polymer or copolymerizing asilicon-containing monomer is proposed for the fluoroalkyl alkyl grouphaving at most 4 carbon atoms to give both good water- andoil-repellency and feeling (for example, WO2004-108855). The increase ofthe silicone polymer content, however, problematically decreases thewater- and oil-repellency.

A fluorine-containing acrylate polymer is disclosed in WO 2006/121171.The fluorine-containing acrylate polymer is dispersed in water by usingan ionic surfactant. The dispersion does not have sufficient propertiessuch as durability of washing durability of water- and oil-repellencyand soil resistance

Problems to be Solved by the Invention

An object of the present invention is to provide a water- andoil-repellent agent comprising a fluorine-containing acrylate polymerwhich imparts excellent water- and oil-repellency and soil resistance toa substrate, when the substrate is treated with the water- andoil-repellent agent.

SUMMARY OF THE INVENTION

The present inventors discovered that the above-mentioned object can beachieved by a dispersion of a polymer which is formed from a monomercomprising a fluorine-containing monomer and which is polymerized in thepresence of a functional organopolysiloxane and a nonionic surfactant.

The present invention provides a dispersion of a fluorine-containingpolymer comprising repeating units derived from a monomer comprising afluorine-containing monomer, wherein the fluorine-containing polymer hasa silicone moiety possessed by a functional organopolysiloxane.

The present invention also provides a method of producing afluorine-containing polymer comprising repeating units derived from amonomer comprising a fluorine-containing monomer, wherein the methodcomprises polymerizing the monomer in the presence of a functionalorganopolysiloxane and a nonionic surfactant to give thefluorine-containing polymer.

This invention provides an aqueous dispersion which comprises:

(I) a fluorine-containing polymer comprising repeating units derivedfrom:

(A) a monomer which comprises;

-   -   (a) a fluorine-containing monomer of the formula:

CH₂═C(X)COOYRf,

wherein X is a hydrogen atom, a monovalent organic group, or a halogenatom,

Y is a direct bond or a divalent organic group, and

Rf is a fluoroalkyl group having 1 to 21 carbon atoms,

wherein the monomer is polymerized in the presence of:

(B) a functional organopolysiloxane selected from the group consistingof a mercapto functional organopolysiloxane, a vinyl functionalorganopolysiloxane and a (meth)acrylamide functional organopolysiloxane,and

(II) water; and(III) an emulsifier consisting of a nonionic surfactant.

The present invention also provides a method of producing a method ofproducing an aqueous dispersion of a fluorine-containing polymercomprising

polymerizing:

(A) a monomer which comprises;

(a) a fluorine-containing monomer of the formula:

CH₂═C(X)COOYRf,

wherein

X is a hydrogen atom, a monovalent organic group, or a halogen atom,

Y is a direct bond or a divalent organic group, and

Rf is a fluoroalkyl group having 1 to 21 carbon atoms,

in the presence of;(B) a functional organopolysiloxane selected from the group consistingof a mercapto functional organopolysiloxane, a vinyl functionalorganopolysiloxane and a (meth)acrylamide functional organopolysiloxane,and(III) an emulsifier consisting of a nonionic surfactant.

The fluorine-containing polymer (that is, a fluorosilicone product) ofthe present invention is useful to provide oil repellent properties to avariety of surfaces. When treating textiles, the fluorosilicone of thepresent invention may also provide a softer hand or feel thanconventional fluorocarbon based oil repellent treatments.

The fluorine-containing monomer (a) is preferably a compound of theformula:

CH₂═C(—X)—C(═O)—O—Y—Rf  (I)

wherein X is a hydrogen atom, an linear or branched alkyl group having 1to 21 carbon atoms, a halogen atom (such as a fluorine atom, a chlorineatom, a bromine atom, a iodine atom), a CFX¹X² group (wherein X¹ and X²is a hydrogen atom or a halogen atom (such as a fluorine atom, achlorine atom, a bromine atom or a iodine atom).), a cyano group, alinear or branched fluoroalkyl group having 1 to 21 carbon atoms, asubstituted or unsubstituted benzyl group, or a substituted orunsubstituted phenyl group,Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms, anaromatic or cycloaliphatic group having 6 to 10 carbon atoms,a —CH₂CH₂N(R¹)SO₂— group (wherein R¹ is an alkyl group having 1 to 4carbon atoms.) ora —CH₂ CH(OY¹)CH₂— group (wherein Y¹ is a hydrogen atom or an acetylgroup.),Rf is a linear or branched fluoroalkyl group having 1 to 21 carbonatoms.

EFFECTS OF THE INVENTION

According to the present invention, when a substrate is treated, thewater- and oil-repellent agent comprising the fluorine-containingacrylate polymer can impart the excellent water- and oil-repellency andsoil resistance to the substrate. When the substrate is a textile, thetreated textile has good feeling. High washing durability of water- andoil-repellency and soil resistance can be obtained.

MODE FOR CARRYING OUT THE INVENTION

In the present invention, the monomer (A) forming thefluorine-containing polymer comprises:

(a) a fluorine-containing monomer,(b) optionally present, a fluorine-free monomer other than acrosslinkable monomer, and(c) optionally present, a crosslinkable monomer.

The fluorine-containing polymer may be a homopolymer formed from onemonomer or a copolymer formed from at least two monomers.

The homopolymer has the repeating units derived from thefluorine-containing monomer (a). The copolymer may has the repeatingunits derived from at least two fluorine-containing monomers (a), or mayhave, in addition to the repeating units derived from thefluorine-containing monomer (a), the repeating units derived from thefluorine-free monomer (b) and optionally the crosslinkable monomer (c).

The fluorine-containing polymer can be prepared by polymerizing themonomer (A) in the presence of the functional organopolysiloxane (B).

The fluorine-containing polymer constituting the surface treatment agentof the present invention comprises:

(a) the fluorine-containing monomer, andoptionally (b) the fluorine-free monomer other than the crosslinkablemonomer, andoptionally (c) the crosslinkable monomer.

(A) Monomer (a) Flourine-containing Monomer

The Component (a) of the present invention is a fluorine-containingmonomer of the formula:

CH₂═C(X)COO—Y—Rf

where Rf is a fluoroalkyl group having 1 to 21 carbon atoms,X is a hydrogen atom, a monovalent organic group, or a halogen atom, andY is a direct bond or a divalent organic group. Y may be for example alinear or branched alkylene group having 1 to 20 carbon atoms, forexample a group of the formula —(CH₂)_(x)— where x is 1 to 10, a groupof the formula —SO₂N(R¹)R²— or of the formula —CON(R¹)R²—, where R¹ isan alkyl group having 1 to 10 carbon atoms and R² is a linear orbranched alkylene group having 1 to 10 carbon atoms, or a group of theformula —CH₂CH(OR³)CH₂— where R³ represents a hydrogen atom or an acylgroup having 1 to 10 carbon atoms such as formyl or acetyl, or a groupof the formula —Ar—CH₂— where Ar is an arylene group optionally having asubstituent. X may be for example H, Me (methyl group), Cl, Br, I, F,CN, CF_(3.)

The fluorine-containing monomer (a) is preferably a compound of theformula:

CH₂═C(—X)—C(═O)—O—Y—Rf  (I)

wherein X is a hydrogen atom, an linear or branched alkyl group having 1to 21 carbon atoms, a halogen atom (such as a fluorine atom, a chlorineatom, a bromine atom, a iodine atom), a CFX¹X² group (wherein X¹ and X²is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom ora iodine atom.), a cyano group, a linear or branched fluoroalkyl grouphaving 1 to 21 carbon atoms, a substituted or unsubstituted benzylgroup, or a substituted or unsubstituted phenyl group,Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms, anaromatic or cycloaliphatic group having 6 to 10 carbon atoms,a —CH₂ CH₂N(R¹)SO₂— group (wherein R¹ is an alkyl group having 1 to 4carbon atoms.) ora —CH₂ CH(OY¹)CH₂— group (wherein Y¹ is a hydrogen atom or an acetylgroup.),Rf is a linear or branched fluoroalkyl group having 1 to 21 carbonatoms.

The alpha-position of the fluorine-containing monomer may be substitutedwith a halogen atom or the like. Accordingly, in the formula (I), X maybe an linear or branched alkyl group having 2 to 21 carbon atoms, afluorine atom, a chlorine atom, a bromine atom, a iodine atom, a CFX¹X²group (wherein X¹ and X² is a hydrogen atom, a fluorine atom, a chlorineatom, a bromine atom or a iodine atom.), a cyano group, a linear orbranched fluoroalkyl group having 1 to 21 carbon atoms, a substituted orunsubstituted benzyl group, or a substituted or unsubstituted phenylgroup.

In the formula (I), the Rf group is preferably a perfluoroalkyl group.The carbon number of the Rf group is from 1 to 21, for example, from 1to 6, particularly from 1 to 5, especially from 1 to 4.

Y is preferably an aliphatic group having 1 to 10 carbon atoms, anaromatic group or cycloaliphatic group having 6 to 10 carbon atoms, a—CH₂CH₂N(R¹)SO₂— group (R¹ is an alkyl group having 1 to 4 carbonatoms.) or a —CH₂CH(OY¹)CH₂— group (Y¹ is a hydrogen atom or an acetylgroup.). The aliphatic group is preferably an alkylene group(particularly the carbon number is from 1 to 4, for example, 1 or 2.).The aromatic group and cycloaliphatic group may be substituted orunsubstituted.

The examples of the fluorine-containing monomer (a) are as follows:

wherein Rf is a linear or branched fluoroalkyl group having, forexample, 1 to 6 carbon atoms.

Other representative non-limiting examples of the fluorine-containingmonomer (a) include the followings:

-   CF₃(CF₂)₇(CH₂)₂OCOCH═CH₂-   CF₃(CF₂)₇(CH₂)₂OCOC(CH₃)═CH₂-   CF₃(CF₂)₇(CH₂)₁₀OCOCH═CH₂-   CF₃(CF₂)₇(CH₂)₁₀OCOC(CH₃)═CH₂-   CF₃(CF₂)₆CH₂OCOCH═CH₂-   CF₃(CF₂)₈CH₂OCOCH═CH₂-   (CF₃)₂CF(CF₂)₆(CH₂)₂OCOCH═CH₂-   (CF₃)₂CF(CF₂)₈(CH₂)₂OCOCH═CH₂-   (CF₃)₂CF(CF₂)₁₀(CH₂)₂OCOCH═CH₂-   (CF₃)₂CF(CF₂)₆(CH₂)₂OCOC(CH₃)═CH₂-   (CF₃)₂CF(CF₂)₈(CH₂)₂OCOC(CH₃)═CH₂-   (CF₃)₂CF(CF₂)₁₀(CH₂)₂OCOC(CH₃)═CH₂-   CF₃(CF₂)₉(CH₂)₂OCOCH═CH₂-   CF₃(CF₂)₉(CH₂)₂OCOCH═CH₂-   CF₃(CF₂)₁₁(CH₂)₂OCOCH═CH₂-   CF₃(CF₂)₁₁(CH₂)₂OCOC(CH₃)═CH₂-   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOCH═CH₂-   CF₃(CF₂)₇SO₂N(C₂H₅)(CH₂)₂OCOCH═CH₂-   (CF₃)₂CF(CF₂)₈CH₂CH(OCOCH₃)CH₂OCOC(CH₃)═CH₂

(CF₃)₂CF(CF₂)₆CH₂CH(OH)CH₂OCOCH═CH₂

-   C₈F₁₇—O-Ph-CH₂OCOCH═CH₂ (where Ph represents 1,4-phenylene)-   C₅F₁₁—O-Ph-CH₂OCOC(CH₃)═CH₂-   C₈F₁₇—O-Ph-COOCH₂CH(OH)CH₂OCOC(CH₃)═CH₂-   (CF₃)₂CFOCOC(CH₃)═CH₂-   (CF₃)₂CF(CH₂)₂OCOC(CH₃)═CH₂-   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOC(F)═CH₂-   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOC(Cl)═CH₂-   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOC(Br)═CH₂-   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOC(I)═CH₂-   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOC(CF₃)═CH₂-   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOC(CN)CH₂-   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOC(C₆H₅)═CH₂-   CF₃(CF₂)₇(CH₂)₂OCOC(F)═CH₂-   CF₃(CF₂)₇(CH₂)₂OCOC(Cl)═CH₂-   CF₃(CF₂)₇(CH₂)₂OCOC(Br)═CH₂-   CF₃(CF₂)₇(CH₂)₂OCOC(I)═CH₂-   CF₃(CF₂)₇(CH₂)₂OCOC(CF₃)═CH₂-   CF₃(CF₂)₇(CH₂)₂OCOC(CN)═CH₂-   CF₃(CF₂)₇(CH₂)₂OCOC(C₆H₅)═CH₂

(b) Fluorine-Free Monomer

The fluorine-containing polymer may have the repeating units derivedfrom the fluorine-free monomer (b). The fluorine-free monomer (b) isother than the crosslinkable monomer (c). The monomer (b) is preferablya fluorine-free monomer having a carbon-carbon double bond. The monomer(b) is preferably a vinyl monomer which is free from fluorine. Thefluorine-free monomer (b) is generally a compound having onecarbon-carbon double bond. Preferable examples of the fluorine-freemonomer (b) include, for example, ethylene, vinyl acetate, vinyl halidesuch as vinyl chloride, vinylidene halide such as vinylidene chloride,acrylonitrile, styrene, polyethyleneglycol (meth)acrylate,polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol(meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, vinyl alkylether and isoprene. The fluorine-free monomer (b) is not limited tothese examples. The fluorine-free monomer (b) may contain vinyl halideand/or vinylidene halide.

The fluorine-free monomer (b) may be a (meth)acrylate ester having analkyl group. The number of carbon atoms of the alkyl group may be from 1to 30, for example, from 6 to 30, e.g., from 10 to 30. For example,fluorine-free monomer (b) may be acrylates of the general formula:

CH₂═CA¹COOA²

wherein A¹ is a hydrogen atom, a methyl group, or a halogen atom (forexample, a chlorine atom, a bromine atom and a iodine atom) other than afluorine atom, and A² is a hydrocarbon group having 1 to 30 carbonatoms, particularly an alkyl group represented by C_(n)H_(2n+1) (n=1 to30).

(c) Crosslinkable Monomer

The fluorine-containing polymer may contain the repeating units derivedfrom the crosslinkable monomer (c). The crosslinkable monomer (c) may bea fluorine-free vinyl monomer having at least two reactive groups and/orcarbon-carbon atoms. The crosslinkable monomer (c) may be a compoundhaving at least two carbon-carbon double bonds, or a compound having atleast one carbon-carbon double bond and at least one reactive group.Examples of the reactive group include a hydroxyl group, an epoxy group,a chloromethyl group, a blocked isocyanate group, an amino group and acarboxyl group.

Examples of the crosslinkable monomer (c) include diacetoneacrylamide,(meth)acrylamide, N-methylolacrylamide, hydroxymethyl(meth)acrylate,hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate,N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, butadiene, chloroprene and glycidyl(meth)acrylate,to which the crosslinkable monomer is not limited.

The copolymerization with the monomer (b) and/or the monomer (c) canoptionally improve various properties such as water repellency and soilresistance; cleaning durability and washing durability of saidrepellency and resistance; solubility in solvent; hardness; and feeling.

In the fluorine-containing polymer,

the amount of the fluorine-free monomer (b) may be from 0.1 to 100 partsby weight, for example, from 0.1 to 50 parts by weight, andthe amount of the crosslinkable monomer (c) may be at most 50 parts byweight, for example, at most 20 parts by weight, particularly, from 0.1to 15 parts by weight, based on 100 parts by weight of thefluorine-containing monomer (a).

The monomer (A) can be polymerized in the presence of the mercapto,vinyl or (meth)acrylamide functional organopolysiloxane (B). Examples ofan olefinically unsaturated co-monomer included in the monomer (A)include alkyl acrylate or methacrylate esters having 1 to 30 carbonatoms in the alkyl group such as butyl acrylate, ethyl acrylate, methylacrylate, methyl methacrylate or butyl methacrylate. The alkyl acrylateor methacrylate can be used to adjust the glass transition temperature(Tg) of the resulting polymeric product resulting from the reaction ofthe fluorine-containing monomer (A) and the mercapto, vinyl or(meth)acrylamide functional organopolysiloxane (B); for example anacrylate having a long chain alkyl group of 4-20, particularly 8-20carbon atoms such as stearyl acrylate or methacrylate, octyl acrylate,2-ethylhexyl acrylate or dodecyl acrylate or methacrylate can be used toform a softer polymer of lower Tg. Copolymers with an alkyl acrylate ormethacrylate monomer may improve various properties such as water- andoil-repellency and soil releasability, cleaning durability, washingdurability and abrasion resistance of such repellency and releasability,solubility in solvent, hardness and feel (handle). Other acrylate ormethacrylate comonomers which can be used include polyethylene glycolacrylate or methacrylate, polypropylene glycol acrylate or methacrylate,methoxypolyethylene glycol acrylate or methacrylate andmethoxypolypropylene glycol acrylate or methacrylate. Other olefinicallyunsaturated comonomers which can be used include vinyl chloride,vinylidene chloride, styrene, acrylonitrile, methacrylonitrile,ethylene, a vinyl alkyl ether, isoprene or a vinyl ester such as vinylacetate or vinyl propionate. The olefinically unsaturated comonomer canbe used which contains a functional group that, although not reactivewith amine groups, may be reactive with other functional groups to giveproperties such as increased substantivity on textiles and othersubstrates. Examples of such functional groups are hydroxyl, amino andamide, and examples of olefinically unsaturated comonomers containingthem are acrylamide, methacrylamide, N-methylolacrylamide, hydroxyethylmethacrylate, hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylateor methacrylate, N,N-dimethylaminoethyl acrylate or methacrylate anddiethylaminoethyl acrylate or methacrylate.

(B) The Functional Organopolysiloxane

The functional organopolysiloxane is a mercapto functionalorganopolysiloxane, a vinyl functional organopolysiloxane,(meth)acrylamide functional organopolysiloxane or a mixture thereof. Thefunctional organopolysiloxane (B) functions as a chain transfer agent.By a polymerization reaction, the functional organopolysiloxane (B)bonds to the fluorine-containing polymer though the functional oragnicgroup.

Component (B) of the present invention may be a mercapto functionalorganopolysiloxane, that is, an organopolysiloxane having a mercaptofunctional organic group present in the molecule. As used herein, a“mercapto functional organic group” is any organic group containing asulfur atom, such as —(CH₂)_(n)—SH (n is the number of 0 to 10,particularly 1 to 5).

Component (B) of the present invention may be a vinyl functionalorganopolysiloxane, that is, an organopolysiloxane having a vinylfunctional organic group present in the molecule. As used herein, a“vinyl functional organic group” is a group containing a —CH═CH₂ group,such as —(CH₂)_(n)—CH═CH₂ (n is the number of 0 to 10, particularly 1 to5). The vinyl group-containing silicone (B) (that is, the vinylfunctional organopolysiloxane (B)) is a siloxane compound which has atleast one (for example, 1 to 500, particularly 2 to 50) vinyl group anda silicone moiety having two or more siloxane linkages.

Component (B) of the present invention may be a (meth)acrylamidefunctional organopolysiloxane, that is, an organopolysiloxane having a(meth)acrylamide functional organic group present in the molecule. Theterm “(meth)acrylamide” means acrylamide or methacrylamide. As usedherein, a “(meth)acrylamide functional organic group” is a groupcontaining a —NH—C(═O)—CQ=CH₂ group, such as —(CH₂)_(n)—NH—C(═O)—CQ=CH₂(wherein Q is a hydrogen atom or a methyl group, and n is the number of0 to 10, particularly 1 to 5). The (meth)acrylamide group-containingsilicone (B) (that is, the (meth)acrylamide functionalorganopolysiloxane (B)) is a siloxane compound which has at least one(for example, 1 to 500, particularly 2 to 50) (meth)acrylamide group anda silicone moiety having two or more siloxane linkages.

Organopolysiloxanes are well known in the art and are often designatedby the general formula R_(n)SiO_(4-n/2), where the organopolysiloxanesmay comprise any number of “M” (mono functional) siloxy units(R₃SiO_(0.5)), “D” (difunctional) siloxy units (R₂SiO) “T”(trifunctional) siloxy units (RSiO_(1.5)), or “Q” siloxy units (SiO₂)where R is independently a monovalent organic group. These siloxy unitscan be combined in various manners to form cyclic, linear, or branchedstructures. The chemical and physical properties of the resultingpolymeric structures can vary. For example organopolysiloxanes can bevolatile or low viscosity fluids, high viscosity fluids/gums, elastomersor rubbers, and resins. R is independently a monovalent organic group,alternatively R is a hydrocarbon group containing 1 to 30 carbons,alternatively R is an alkyl group containing 1 to 30 carbon atoms, oralternatively R is methyl.

The organopolysiloxanes useful as component (B) in the present inventionare characterized by having at least one of the R groups in the formulaR_(n)SiO_((4-n)/2) be a mercapto, vinyl or (meth)acrylamide group, oralternatively at least one of the R groups be a mercapto, vinyl or(meth)acrylamide group and one of the R groups be an organofunctionalgroup, or alternatively one of the R groups be an organofunctional groupalso containing a mercapto, vinyl or (meth)acrylamide group. Theorganofunctional group and mercapto, vinyl or (meth)acrylamidefunctional group may be present on any siloxy unit having an Rsubstituent, that is, they may be present on any M, D, or T unit.Typically, the organofunctional groups and mercapto, vinyl or(meth)acrylamide groups are present as a R substituent on a D siloxyunit.

As used herein, “organofunctional group” means an organic groupcontaining any number of carbon atoms, but the group contains at leastone atom other than carbon and hydrogen. Representative examples of suchorganofunctional groups include, amines, amides, sulfonamides,quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones,halogen substituted alkyls and aryls group, to name a few.Alternatively, the organofunctional group is an amino-functional organicgroup.

When the organofunctional group is an amino-functional organic group,the amino-functional organic group is designated in the formulas hereinas R^(N) and is illustrated by groups having the formula: —R¹NHR²,—R¹NR₂ ², or —R¹NHR¹NHR², wherein each R¹ is independently a divalenthydrocarbon group having at least 2 carbon atoms, and R² is hydrogen oran alkyl group. Each R¹ is typically an alkylene group having from 2 to20 carbon atoms. R¹ is illustrated by groups such as; —CH₂CH₂—,—CH₂CH₂CH₂—, —CH₂CHCH₃—, —CH₂CH₂CH₂CH₂—, —CH₂CH(CH₃)CH₂—,—CH₂CH₂CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂CH₂CH₂—, —CH₂CH₂CH(CH₂CH₃)CH₂CH₂CH₂—,—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—, and —CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—. Thealkyl groups R² are as illustrated above for R. When R² is an alkylgroup, it is typically methyl.

Some examples of suitable amino-functional hydrocarbon groups are;—CH₂CH₂NH₂, —CH₂CH₂CH₂NH₂, —CH₂CHCH₃NH, —CH₂CH₂CH₂CH₂NH₂,—CH₂CH₂CH₂CH₂CH₂NH₂, —CH₂CH₂CH₂CH₂CH₂CH₂NH₂, —CH₂CH₂NHCH₃,—CH₂CH₂CH₂NHCH₃, —CH₂(CH₃)CHCH₂NHCH₃, —CH₂CH₂CH₂CH₂NHCH₃,—CH₂CH₂NHCH₂CH₂NH₂, —CH₂CH₂CH₂NHCH₂CH₂CH₂NH₂,—CH₂CH₂CH₂CH₂NHCH₂CH₂CH₂CH₂NH₂, —CH₂CH₂NHCH₂CH₂NHCH₃,—CH₂CH₂CH₂NHCH₂CH₂CH₂NHCH₃, —CH₂CH₂CH₂CH₂NHCH₂CH₂CH₂CH₂NHCH₃, and—CH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂CH₃. Typically, the amino functional group is—CH₂CH₂CH₂NH_(2.)

The mercapto-functional organic group is designated in the formulasherein as R^(s) and is illustrated by groups having the formula: —R¹SR²,wherein each R¹ and R² is as defined above. The mercapto-functionalgroup is illustrated by the following formulae; —CH₂CH₂CH₂SH,—CH₂CHCH₃SH, —CH₂CH₂CH₂CH₂SH, —CH₂CH₂CH₂CH₂CH₂SH, —CH₂CH₂CH₂CH₂CH₂CH₂SH,—CH₂CH₂SCH₃. Typically, the mercapto functional group is —CH₂CH₂CH₂SH.

The vinyl functional organic group is designated in the formulas hereinas R^(V). The vinyl functional organic group is illustrated by thefollowing formulae; —CH═CH₂, —CH₂CH₂CH₂—CH═CH₂, —CH₂CHCH₃—CH═CH₂,—CH₂CH₂CH₂CH₂—CH═CH₂, —CH₂CH₂CH₂CH₂CH₂—CH═CH₂,—CH₂CH₂CH₂CH₂CH₂CH₂—CH═CH₂. Typically, the vinyl functional group is—CH═CH_(2.)

The (meth)acrylamide functional organic group is designated in theformulas herein as R^(A) and is illustrated by groups having theformula: —R¹—NH—C(═O)—CQ=CH₂ group (wherein R¹ is a divalent hydrocarbongroup having at least 2 carbon atoms, and Q is a hydrogen atom or amethyl group). The (meth)acrylamide functional group is illustrated bythe following formulae; —CH₂CH₂CH₂—NH—C(═O)—CH═CH₂,—CH₂CH₂CH₂—NH—C(═O)—C(CH₃)═CH₂, —CH₂CHCH₃—NH—C(═O)—CH═CH₂,—CH₂CHCH₃—NH—C(═O)—C(CH₃)═CH₂, —CH₂CH₂CH₂CH₂—NH—C(═O)—C(CH₃)═CH₂,—CH₂CH₂CH₂CH₂—NH—C(═O)—C(CH₃)═CH₂. Typically, the (meth)acrylamidefunctional group is —CH₂CH₂CH₂—NH—C(═O)—C(CH₃)═CH_(2.)

In a preferable embodiment, the mercapto functional organopolysiloxane(designated B′) comprises siloxy units having the average formula:

(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(S)SiO)_(c)

where;

a is 0-4000, alternatively 0 to 1000, alternatively 0 to 400,

b is 1-1000, alternatively 1 to 100, alternatively 1 to 50,

c is 1-1000, alternatively 1 to 100, alternatively 1 to 50;

R is independently a monovalent organic group,

alternatively R is a hydrocarbon containing 1-30 carbon atoms,

-   -   alternatively R is a monovalent alkyl group containing 1-12        carbons, or        -   alternatively R is a methyl group;            R^(N) is a monovalent amino functional organic group as            defined above,            R^(S) is a monovalent mercapto functional organic group as            defined above.

In a preferable embodiment, the vinyl functional organopolysiloxane(designated B′) comprises siloxy units having the average formula:

(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(V)SiO)_(c)

where;a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400,b is 1-1000, alternatively 2 to 100, alternatively 3 to 50,c is 1-1000, alternatively 2 to 100, alternatively 3 to 50;R each is independently a monovalent organic group,alternatively R each is a hydrocarbon containing 1-30 carbon atoms,alternatively R each is a monovalent alkyl group containing 1-12carbons, oralternatively R each is a methyl group;R^(N) each is a monovalent amino functional organic group as definedabove,R^(V) each is a vinyl functional organic group as defined above.

In a preferable embodiment, the (meth)acrylamide functionalorganopolysiloxane (designated B′) comprises siloxy units having theaverage formula:

(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(A)SiO)_(c)

wherein R^(A) each is a (meth)acrylamide functional organic group asdefined above, and other symbols are the same as defined above.

The R^(N) group may be R^(F) wherein R^(F) may be a monovalentorganofunctional organic group as defined above, such as hydroxyls,amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols,esters, carboxyls, ketones, halogen-substituted alkyls and aryls group.For example, the vinyl functional organopolysiloxane may comprise siloxyunits having the average formula:

(R₂SiO)_(a)(RR^(F)SiO)_(b)(RR^(V)SiO)_(c)

wherein the groups and subscripts (that is, a, b and c) are the samedefine above.

Organopolysiloxane (B′) may be terminated with a hydrogen atom(resulting in a silanol group on the terminal siloxy unit of theterpolymer), or with an alkyl group containing 1-30 carbon atoms(resulting in an alkoxy group on the terminal siloxy unit of theterpolymer). When an alkyl group is used, the alkyl group can be alinear or branched alkyl, containing 1-30 carbons, alternatively thealkyl group can be a long chain alkyl group of 4-20, alternatively 8-20carbon atoms such as stearyl. Alternatively the organopolysiloxane canbe terminated with a trimethylsilyl group.

The organopolysiloxane (B′) of this preferable embodiment can berepresented by the following average formula for example;

where;

a is 0-4000, alternatively 0 to 1000, alternatively 0 to 400,

b is 1-1000, alternatively 1 to 100, alternatively 1 to 50,

c is 1-1000, alternatively 1 to 100, alternatively 1 to 50;

and R′ is independently H, an alkyl group having 1 to 40 carbon atoms,or Me₃Si.

The amino-mercapto functional organopolysiloxane terpolymers of thispreferable embodiment (B′) can be prepared by any technique known in theart for preparation of organopolysiloxane terpolymers containing aminoand/or mercapto functional groups. Typically, the organopolysiloxanes(B′) are prepared via a condensation polymerization reaction of an aminofunctional alkoxy silane, a mercapto functional silane monomer, andorganopolysiloxane having alkoxy or silanol termination as illustratedby the following general reaction scheme.

Condensation organopolysiloxanes are well known in the art and aretypically catalyzed by the addition of a strong base, such as analkaline metal hydroxide or a tin compound. Alternativelyco-polymerization of the functionalized cyclosiloxanes could be used.

The vinyl group-containing silicone (B) is of, for example, the formula:

wherein R¹ is a methyl group, a methoxy group, a phenyl group, or ahydroxyl group,R² is a methyl group, a methoxy group, a phenyl group, or a hydroxylgroup,R³ is a methyl group, a methoxy group, a phenyl group, or a hydroxylgroup,R′ is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, orMe₃Si,A is a divalent saturated hydrocarbon group having 1-10 carbon atomswhich may be interrupted with one or two ether linkages,B is a divalent saturated hydrocarbon group having 1-10 carbon atomswhich may be interrupted with one or two ether linkages,C is hydroxyls, amines, amides, sulfonamides, quaternaries, ethers,epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkylsor aryls group,a, b, and c are integers showing the number of repeat units, a is from 1to 4000, for example, 2 to 2000, b is from 1 to 1000, preferably from 2to 800, and c is from 0 to 1000, preferably from 1 to 800.

The example of vinyl group-containing silicone (B) is as follows.

wherein the groups such as the R¹ group and the subscripts are definedas the same as above-mentioned.

The functional group C is particularly preferably an amino group (thatis, the vinyl group-containing silicone (B) is a vinylamino silicone).The amino group has the effect of remarkably improving the affinity withother materials constituting the cosmetic and with a human body skin.

The organopolysiloxane (B′) of the above-mentioned preferable embodimentcan be represented by the following average formula for example;

where;a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400,b is 1-1000, alternatively 2 to 100, alternatively 3 to 50,c is 1-1000, alternatively 2 to 100, alternatively 3 to 50;and R′ is independently H, an alkyl group having 1 to 40 carbon atoms,or Me₃Si.

The vinylamino functional organopolysiloxane terpolymers of thispreferable embodiment (B′) can be prepared by any technique known in theart for preparation of organopolysiloxane terpolymers containing aminoand/or vinyl functional groups. Typically, the organopolysiloxanes (B′)are prepared via a condensation polymerization reaction of an aminofunctional alkoxy silane, a vinyl functional silane monomer, andorganopolysiloxane having alkoxy or silanol termination as illustratedby the following general reaction scheme.

Condensation organopolysiloxanes are well known in the art and aretypically catalyzed by the addition of a strong base, such as analkaline metal hydroxide or a tin compound. Alternativelyco-polymerization of the functionalized cyclosiloxanes could be used.

Typically, the (meth)acrylamide functional organopolysiloxane can beprepared by reacting the amino functional organopolysiloxane with(meth)acrylic anhydride. In the reaction, an amino group (—NH₂) isconverted into an (meth)acrylamide group ((—NH—C(═O)—CQ=CH₂ (wherein Qis a hydrogen atom or a methyl group)). For example, the(meth)acrylamide functional organopolysiloxane may have a≡Si—(CH₂)_(n)—NH—C(═O)—CQ=CH₂ group (wherein Q is a hydrogen atom or amethyl group, and n is the number of 0 to 10, particularly 1 to 5)

The fluorine-containing polymer may have a weight-average molecularweight of 2,000 to 5,000,000, particularly 3,000 to 5,000,000,especially 10,000 to 1,000,000. The weight-average molecular weight (interms of polystyrene) of the fluorine-containing polymer can bedetermined by GPC (Gel Permeation Chromatography).

The fluorine-containing polymer of the present invention can be producedby emulsion polymerization.

In the following preparations of the fluorine-containing polymer, thevinyl silicone and/or acrylamide silicone can be used in place of or inaddition to the mercapto silicone.

In the case of the emulsion polymerization, the polymerization iscarried out in the same manner as described above after emulsifying amixture of the monomers and the mercapto silicone in water using aproper emulsifier. In some combinations of the monomers (a) to (c) andthe mercapto silicone, a poor compatibility of the monomers and themercapto silicone in water results in a poor copolymerizability. In sucha case, a method in which a proper auxiliary solvent such as glycols andalcohols and/or a low molecular weight monomer is added to improve thecompatibility of the mixture is adopted. A hydrophobic group in theemulsifier to be used in the emulsion polymerization may be any ofhydrocarbon type, silicon-containing type and fluorine-containing type.As for the ionicity of a hydrophilic group, nonionic one is used. As thepolymerization initiator for emulsion polymerization, for example,water-soluble initiators (e.g., benzoyl peroxide, lauroyl peroxide,t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide,3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidinedihydrochloride, azobisisobutyronitrile, sodium peroxide, potassiumpersulfate and ammonium persulfate) and oil-soluble initiators (e.g.,azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, laurylperoxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropylperoxydicarbonate) are used. The polymerization initiator may be used inthe amount within the range from 0.01 to 10 parts by weight based on 100parts by weight of the monomers.

In the emulsion polymerization, there can be used a method ofemulsifying monomers in water in the presence of a polymerizationinitiator and an emulsifying agent, replacing the atmosphere bynitrogen, and polymerizing with stirring, for example, at thetemperature within the range from 30 degrees C. to 120 degrees C., forexample, from 50 degrees C. to 80 degrees C., for 1 hour to 10 hours.

When the monomers are not completely compatibilized, a compatibilizingagent capable of sufficiently compatibilizing them (e.g., awater-soluble organic solvent and a low-molecular weight monomer) ispreferably added to these monomers. By the addition of thecompatibilizing agent, the emulsifiability and polymerizability can beimproved.

Examples of the water-soluble organic solvent include acetone, methylethyl ketone, ethyl acetate, propylene glycol, dipropylene glycolmonomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.The water-soluble organic solvent may be used in the amount within therange from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight,based on 100 parts by weight of water. Examples of the low-molecularweight monomer are methyl methacrylate, glycidyl methacrylate,2,2,2-trifluoroethyl methacrylate. The low-molecular weight monomer maybe used in the amount within the range from 1 to 50 parts by weight,e.g., from 10 to 40 parts by weight, based on 100 parts by weight oftotal of monomers.

In the present invention, the nonionic surfactant is used for thepurpose of intimately dispersing the fluorine-containing polymer intothe aqueous dispersion liquid. In the present invention, the use of anionic surfactant is preferably excluded.

The nonionic surfactant may have a hydrophobic group which may be ahydrocarbon, a silicone or a fluorine-containing compound, and ahydrophilic group which is nonionic. The nonionic surfactant may be acompound having at least one (for example, 3 to 300) oxyalkylene group.The alkylene moiety in the oxyalkylene group may have 2 to 5 carbonatoms, preferable 2 or 3 carbon atoms. Preferably, the oxyalkylene groupis an oxyethylene group and/or an oxypropylene group.

The nonionic surfactant includes an oxyalkylene compound of the formula:

R¹O[CH₂CH(CH₃)O]_(a)—(CH₂CH₂O)_(b)—R²  (S)

wherein R¹ is a linear or branched alkyl or alkenyl group,R² is a hydrogen atom or a linear or branched alkyl or alkenyl group,a is an integer of 0 to 300, andb is an integer of 0 to 300, provided that the total of a and b is from1 to 400. The oxypropylene group and oxyethylene group may be or may notbe positioned in the order shown in the formula (S), and may form arandom copolymer or a block copolymer.

R¹ may be the linear alkyl or alkenyl group having 1 to 30 carbon atoms,or the branched alkyl or alkenyl group having 3 to 30 carbon atoms. Thebranched alkyl or alkenyl group is preferably the group wherein a mainchain has at least 5 carbon atoms and a side chain has at least 3 carbonatoms.

Preferably, the side chain is the alkyl group and the number of the sidechains is at least 3, for example, at least 4. The side chain, which isthe alkyl group, may be an alkyl group having 1 to 3 carbon atoms,particularly a methyl group. The alkyl or alkenyl group preferably hasat least 10 carbon atoms. The upper limit of the carbon atom number ofthe alkyl or alkenyl group may be 50, for example, 30.

R¹ (and optionally R²) is particularly preferably a C₁₃ isotridecylgroup having 4 side-chain methyl groups, that is,CH₃CH(CH₃)CH₂CH(CH₃)CH₂CH(CH₃)CH₂CH(CH₃)CH₂—, or a C₁₃ isotridecyl grouphaving 6 side-chain methyl groups, that is,CH₃C(CH₃)₂CH₂C(CH₃)₂CH₂C(CH₃)₂CH₂—, orCH₂(CH₃)CH(CH₃)CH(CH₃)CH(CH₃)CH(CH₃)CH(CH₃)CH₂—, or a C₁₃ isotridecylgroup having 3 side-chain ethyl groups, that is,CH₃CH(C₂H₅)CH₂CH(C₂H₅)CH₂CH(C₂H₅)CH₂—.

R² is preferably a hydrogen atom, but may be the linear or branchedalkyl or alkenyl group as discussed above.

In the formula, “a” is at least 0, for example, at least 3, preferably 5to 200, and “b” is at least 0, for example, at least 3, preferably 5 to200. Preferably, the total of “a” and “b” is from 3 to 300, for example,from 5 to 200.

The nonionic surfactant may be one or a combination of at least two. Atleast two nonionic surfactants may be used. Preferable combination oftwo nonionic surfactants includes:

(1) at least two oxyalkylene compounds of the formula (S);

(2) the oxyalkylene compound of the formula (S) with the nonionicsurfactant other than the oxyalkylene compound of the formula (S); and

(3) at least two nonionic surfactants other than the oxyalkylenecompound of the formula (S).

Preferable is the combination of the oxyalkylene compound of the formula(S) wherein R¹ is a branched alkyl or alkenyl group and R² is a hydrogenatom with the oxyalkylene compound of the formula (S) wherein R¹ is alinear alkyl or alkenyl group and R² is a hydrogen atom.

Specific examples of the nonionic surfactant used in the presentinvention include polyoxyethylene lauryl ether, polyoxyethylene tridecylether, polyoxyethylene cetyl ether, polyoxyethylene polyoxypropylenecetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether,polyoxyethylene monolaurate, polyoxyethylene monostearate,polyoxyethylene mono-oleate, sorbitan monolaurate, sorbitanmonostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitanmono-oleate, sorbitan sesqui-oleate, sorbitan trioleate, polyoxyethylenesorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitanmono-oleate, polyoxyethylene polyoxypropylene block polymer,polyglycerin fatty acid ester, polyether-modified silicone oil (SH3746,SH3748, SH3749 and SH3771 manufactured by Toray Dow Corning SiliconeCo., Ltd.), perfluoroalkyl ethylene oxide adduct (UNIDYNE DS-401 andDS-403 manufactured by Daikin Industries, Ltd.), fluoroalkyl ethyleneoxide adduct (UNIDYNE DS-406 manufactured by Daikin Industries, Ltd.),and perfluoroalkyl oligomer (UNIDYNE DS-451 manufactured by DaikinIndustries, Ltd.).

Examples of the commercially available product of the nonionicsurfactant includes polyoxyethylene oleyl ether (trade name: EMULGEN430, manufactured by Kao Corporation), polyoxyethylene lauryl ether(trade name: NIKKOL BL-21, manufactured by Nikko Chemicals Co., Ltd.).The nonionic surfactant may be used alone or a combination of at leasttwo.

Other examples of the nonionic surfactant include a condensate productof ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleicacid, alkane(C₁₂₋₁₆) thiol, and sorbitan monofatty acid(C₇₋₁₉) oralkyl(C₁₂₋₁₈) amine.

The nonionic surfactant may be used in the amount within the range from0.1 to 20 parts by weight, preferably from 0.5 to 10 parts by weight,based on 100 parts by weight of the monomers or polymer. The nonionicsurfactant may be added before or after the polymerization.

In order to obtain a polymer dispersion in water, which has a highpolymer solid content and which has very fine and stable particles, itis desirable that the mixture of the monomers and the mercapto siliconeis dispersed in water by using an emulsifying device capable of applyinga strong shearing energy (e.g., a high-pressure homogenizer and anultrasonic homogenizer) to prepare the fine particles of the mixture,and then the polymerization is conducted.

The fluorosilicone reaction product of the fluorine-containing monomer(A) and the mercapto organopolysiloxane (B) may be prepared by anyreaction process known in the art to effect polymerisation of suchmonomers. Preferably, the fluorosilicone may be prepared according tothe process of the present invention comprising;

I) reacting,

(A) a monomer comprising a fluorine-containing monomer of the formula:

CH₂═C(X)COOYRf,

-   -   X is a hydrogen atom, a monovalent organic group, or a halogen        atom,    -   Y is a direct bond or a divalent organic group having 1 to 20        carbon atoms, and    -   Rf is a fluoroalkyl group having 1 to 21 carbon atoms,        in the presence of

(B) a functional organopolysiloxane selected from the group consistingof a mercapto functional organopolysiloxane, a vinyl functionalorganopolysiloxane and a (meth)acrylamide functional organopolysiloxane,via a polymerization reaction, preferably a free radical polymerisationreaction.

Components (A) and (B) in the process are the same as described above.

The process may also be conducted in the presence of a polar organicsolvent. The polar organic solvent can be one or more alcohol, ketone orester solvents selected from butanol, t-butanol, isopropanol,butoxyethanol, methyl isobutyl ketone, methyl ethyl ketone, butylacetate or ethyl acetate and/or an aromatic hydrocarbon such as xylene,toluene or trimethylbenzene a blend of one or more of these.

The initiator for the free radical polymerisation reaction can be anycompound known in the art for initiating free radical reactions, such asorganic peroxides or azo compounds. Representative, non-limitingexamples are; azo compounds such as azobisisobutyronitrile orazobisisovaleronitrile (AIVN), peroxides such as benzoyl peroxide. Thepolymerisation temperature typically ranges 50-120° C.

Alternatively the polymeric reaction product can be obtained using thetechnique of emulsion polymerisation, where all the components arepolymerised in the presence of water, surfactants and polymerisationinitiator.

The fluorosilicone reaction product can contain various ratios of thefluorine-containing monomer (A) and the functional organopolysiloxane(B), as controlled by the amount of each of components (A) and (B). Thefluorosilicone may contain 5 to 99.9% by weight, preferably 10 to 95% byweight of the monomer (A), and 0.1 to 95% by weight, preferably 5 to 90%by weight of the functional organopolysiloxane (B) with the proviso thatsum of the wt % of (A) and (B) equals 100%. A fluorosilicone producthaving a high proportion of functional organopolysiloxane may providegreater substantivity to fibrous substrates or softness of handle of thetreated material. A polymeric product having a high proportion offluorine-containing monomer may provide maximum hydrophobicity andoleophobicity.

The emulsion is generally used, diluted as required, without isolatingthe polymeric product.

The emulsion of fluorosilicone reaction product can be applied tofibrous substrates such as textiles by any of the methods known fortreatment of textiles with liquids. The concentration of thefluorosilicone reaction product in the liquid applied to the textile canfor example be 0.5 to 20% by weight, alternatively 1 to 5%. When thetextile is a fabric, the fabric can be immersed in the liquid or can bepadded or sprayed with the liquid. The treated textile is dried and ispreferably heated, for example at 100-200° C., to develop the oilrepellency.

Alternatively, the fluorosilicone reaction product can be applied to atextile via a cleaning process, such as in a laundry application or drycleaning process.

The textile which is treated is typically a fabric, including woven,knitted and nonwoven fabrics, fabrics in garment form and carpet, butmay also be a fibre or yarn or intermediate textile product such as asliver or roving. The textile material can be a natural fibre such ascotton or wool, a manmade fibre such as viscose rayon or lyocell or asynthetic fibre such as polyester, polyamide or acrylic fibre, or can bea mixture of fibres such as a mixture of natural and synthetic fibres.The polymeric product of the invention is particularly effective inrendering cellulosic fibres such as cotton or rayon oleophobic and oilrepellent. The process of the invention generally also renders thetextile hydrophobic and water repellent. Fabric treatment with thepolymeric product of the invention imparts oil repellency to fabricswhilst at the same time imparting an improvement in feel compared tountreated fabric and also imparting an improvement in feel compared tofabric treated with known fluoropolymer textile treatment agents.

The fibrous substrate can alternatively be leather. The polymericproduct can be applied to leather from aqueous emulsion at variousstages of leather processing, for example during leather wet endprocessing or during leather finishing, to render the leatherhydrophobic and oleophobic.

The fibrous substrate can alternatively be paper. The polymeric productcan be applied to preformed paper or at various stages of papermaking,for example during drying of the paper.

The surface treatment agent of the present invention is preferably inthe form of an emulsion or an aerosol. The surface treatment agentgenerally comprises the fluorine-containing polymer and a medium(particularly a liquid medium, for example, an organic solvent and/orwater). The concentration of the fluorine-containing polymer in thesurface treatment agent may be, for example, from 0.1 to 50% by weight.

The surface treatment agent can be applied to a substrate to be treatedby a know procedure. The application of the surface treatment agent canbe conducted by immersion, spraying and coating. Usually, the surfacetreatment agent is diluted with an organic solvent or water, is adheredto surfaces of the substrate by a well-known procedure such as animmersion coating, a spray coating and a foam coating, and is dried. Ifnecessary, the treatment liquid is applied together with a suitablecrosslinking agent, followed by curing. It is also possible to addmothproofing agents, softeners, antimicrobial agents, flame retardants,antistatic agents, paint fixing agents, crease-proofing agents, etc. tothe surface treatment agent. The concentration of thefluorine-containing compound in the treatment liquid contacted with thesubstrate may be from 0.01 to 10% by weight (particularly for immersioncoating), for example, from 0.05 to 10% by weight (particularly forspray coating), based on the treatment liquid.

The substrate to be treated with the surface treatment agent (forexample, a water- and oil-repellent agent) of the present invention ispreferably a textile. The textile includes various examples. Examples ofthe textile include animal- or vegetable-origin natural fibers such ascotton, hemp, wool and silk; synthetic fibers such as polyamide,polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride andpolypropylene; semisynthetic fibers such as rayon and acetate; inorganicfibers such as glass fiber, carbon fiber and asbestos fiber; and amixture of these fibers.

The textile may be in any form such as a fiber, a yarn and a fabric.

The term “treatment” means that the treatment agent is applied to thesubstrate by immersion, spray, coating or the like. Thefluorine-containing polymer which is an active component of thetreatment agent can penetrate the internal of the substrate or canadhere on the surface of the substrate by the treatment.

EXAMPLES

The following Preparative Examples and Examples further illustrate thepresent invention in detail but are not to be construed to limit thescope thereof. All parts and percentages in the examples are on a weightbasis and all measurements were obtained at about 23° C., unlessindicated to the contrary.

1. Shower Water Repellency Test (JIS-L-1092)

Shower water repellency test was conducted according to JIS-L-1092. Theshower water repellency was expressed by water repellency No. (as shownin the below-described Table 1).

A glass funnel which has a volume of at least 250 ml and a spray nozzlewhich can spray 250 ml of water for 20-30 seconds are used. A test pieceflame is a metal flame having a diameter of 15 cm. Three sheets of atest piece having a size of about 20 cm×20 cm are prepared and the sheetis mounted on a test piece holding flame so that the sheet has nowrinkle. The center of the spray was located on the center of the sheet.Room temperature water (250 mL) is charged into the glass funnel andsprayed on the test piece sheet (for time of 25-30 seconds). The holdingflame is removed from a stand, one edge of the holding flame is graspedso that a front surface is downside and the other edge is lightly hitwith a stiff substance. The holding flame is further rotated 180° andthe same procedure is repeated to drop excess water droplets. The wettest piece is compared with a wet comparison standard to grade 0, 50,70, 80, 90 and 100 points in order of poor water-repellency to excellentwater repellency. The results are obtained from an average of threemeasurements.

TABLE 1 Water repellency No. State 100 No wet or water droplets adhesionon surface 90 No wet but small water droplets adhesion on surface 80Separate small water droplets-like wet on surface 70 Wet on half ofsurface and separate small wet which penetrates fabric 50 Wet on wholesurface 0 Wet on front and back whole surfaces

2. Water-Repellency Test (According to AATCC Test Method 118-1992)

A treated fabric is stored in a thermo-hygrostat having a temperature of21° C. and a humidity of 65% for at least 4 hours. A test liquid(isopropyl alcohol (IPA), water, and a mixture thereof, as shown inTable 2) which has been also stored at 21° C. is used. The test isconducted in an air-conditioned room having a temperature of 21° C. anda humidity of 65%. Five droplets of the test liquid wherein one droplethas an amount of 50 μL are softly dropped by a micropipette on thefabric. If 4 or 5 droplets remain on the fabric after standing for 30seconds, the test liquid passes the test. The water-repellency isexpressed by a point corresponding to a maximum content of isopropylalcohol (% by volume) in the test liquid which passes the test. Thewater-repellency is evaluated as twelve levels which are Fail, 0, 1, 2,3, 4, 5, 6, 7, 8, 9 and 10 in order of a bad level to an excellentlevel.

TABLE 2 Water-repellency test liquid (% by volume) Point Isopropylalcohol Water 10 100 0 9 90 10 8 80 20 7 70 30 6 60 40 5 50 50 4 40 60 330 70 2 20 80 1 10 90 0 0 100 Fail Inferior to isopropyl alcohol 0/water100

3. Oil-Repellency Test (According to AATCC Test Method 118-1992)

A treated fabric is stored in a thermo-hygrostat having a temperature of21° C. and a humidity of 65% for at least 4 hours. A test liquid (shownin Table 3) which has been also stored at 21° C. is used. The test isconducted in an air-conditioned room having a temperature of 21° C. anda humidity of 65%. Five droplets of the test liquid wherein one droplethas an amount of 50 μL are softly dropped by a micropipette on thefabric. If 4 or 5 droplets remain on the fabric after standing for 30seconds, the test liquid passes the test. The oil-repellency isexpressed by a maximum point of the test liquid which passes the test.The oil-repellency is evaluated as nine levels which are Fail, 1, 2, 3,4, 5, 6, 7 and 8 in order of a bad level to an excellent level.

TABLE 3 Oil-repellency test liquid Surface tension Point Test liquid(dyne/cm, 25° C.) 8 n-Heptane 20.0 7 n-Octane 21.8 6 n-Decane 23.5 5n-Dodecane 25.0 4 n-Tetradecane 26.7 3 n-Hexadecane 27.3 2 Mixtureliquid of 29.6 n-Hexadecane 35/nujol 65 1 Nujol 31.2 Fail Inferior to 1—

4. Washing Durability of Water- and Oil-Repellency

Washing is conducted repeatedly ten times or twelve times according toJIS L-0217-103 method, and then water- and oil-repellency is evaluated(HL-10, 20).

5. Feeling

The feeling of a treated PET fabric is determined by hand touchaccording to the following criteria.

Very good: Remarkably softer than untreated fabricGood: Same softness as or softer than untreated fabricPoor: Harder than untreated fabric

Synthesis of Amino-Mercapto Functional Siloxanes Siloxane 1

Into a three necked round bottomed flask fitted with a condenser,overhead stirrer and thermocouple were charged a silanol terminatedpolydimethylsiloxane (708 g Mn˜900), mercaptopropylmethyldimethoxysilane(37 g), aminopropylmethyldiethoxysilane (22 g), barium hydroxide (0.5 g)and sodium orthophosphate (0.2 g). The reaction mixture was heated to75° C. and held at this temperature for three hours after whichvolatiles were removed under reduced pressure (200 mbar) at 85° C. forninety minutes. To the crude product was then addedtrimethylethoxysilane (50 g) and the reaction held at 85° C. for afurther three hours followed by further volatile removal at 70° C./50mbar pressure for thirty minutes.

Siloxane 2

Into a three necked round bottomed flask fitted with a condenser,overhead stirrer and thermocouple were charged a silanol terminatedpolydimethylsiloxane (323 g Mn˜900 and 380 g Mn˜300),mercaptopropylmethyldimethoxysilane (230 g),aminopropylmethyldiethoxysilane (27 g), trimethylethoxysilane (42 g),barium hydroxide (0.62 g) and sodium orthophosphate (0.25 g). Thereaction mixture was heated to 75° C. and held at this temperature forthree hours after which volatile removal was carried out at 75° C. and areduced pressure of 200 mbar for four hours.

Siloxane 3

Into a three necked round bottomed flask fitted with a condenser,overhead stirrer and thermocouple were charged a silanol terminatedpolydimethylsiloxane (743 g Mn˜300),mercaptopropylmethyldiethoxysilane(230 g),aminopropylmethyldiethoxysilane (27 g), trimethylethoxysilane (39 g),barium hydroxide (0.62 g) and sodium orthophosphate (0.25 g). Thereaction mixture was heated to 75° C. and held at this temperature forthree hours after which volatile removal was carried out at 75° C. and areduced pressure of 200 mbar for four hours.

The physical and structural properties of the aminomercaptosiloxanes(Siloxane 1, Siloxane 2 and Siloxane 3) are described in the tablebelow:

TABLE A % OR % SiMe₃ or SiOH Viscosity % N % SH End End Batch Mn (cts)(w/w) (w/w) Groups Groups Siloxane 1 11219 477 0.21 0.80 51 49 Siloxane2 4396 74 0.26 4.10 9 91 Siloxane 3 4502 69 0.26 4.49 35 65

Siloxane 4

Into a three necked round bottom flask fitted with a condenser andthermocouple was charged Dow Corning amino-functional siloxane (2-8630)with a nitrogen content of 0.36% w/w and a viscosity of 1560 cP (300 g)and methoxyphenol (3 g). After mixing, methacrylic anhydride (24 g) wasadded to the reaction vessel resulting in small exotherm. After theexotherm had subsided the reaction mixture was heated to 130° C. andunreacted methacrylic anhydride and methacrylic acid was removed underreduced pressure for three hours. The nitrogen content was determined tobe 0.01% w/w on completion of the reaction as determined by titration.Near Infra Red analysis gave a vinyl content for the methacrylamidemodified polymer of 0.414% w/w and the final polymer viscosity was68,950 cP. The methacrylamide modified polymer was of the followingformula:

Preparative Example 1

Into a 1 L autoclave, CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(CH₃)═CH₂ (n=2.0)(184 g), stearyl acrylate (23.1 g), glycerol monomethacrylate (4.3 g),glycidyl methacrylate (1.4 g), Siloxane 1 (aminomercapto silicone) (28.4g), pure water (500 g), tripropylene glycol (79.4 g), polyoxyethylenelauryl ether (18.0 g) and polyoxyethylene isotridecyl ether (7.7 g) werecharged and emulsified by ultrasonic wave at 60° C. for 15 minutes withstirring. After the atmosphere of the autoclave was replaced withnitrogen gas, vinyl chloride (67 g) was injected. Then,2,2′-azobis(2-amidinopropane) dihydrochloride (3.6 g) was added and thereaction was conducted at 60° C. for 5 hours to give an aqueousdispersion of a polymer.

Preparative Example 2

Into a 1 L autoclave, CF₃CF₂—(CP₂CF₂)_(n)—CH₂CH₂OCOC(CH₃)═CH₂ (n=2.0)(184 g), stearyl acrylate (23.1 g), glycerol monomethacrylate (4.3 g),glycidyl methacrylate (1.4 g), Siloxane 4 (methacrylamide silicone)(28.4 g), pure water (500 g), tripropylene glycol (79.4 g),polyoxyethylene lauryl ether (18.0 g) and polyoxyethylene isotridecylether (7.7 g) were charged and emulsified by ultrasonic wave at 60° C.for 15 minutes with stirring. After the atmosphere of the autoclave wasreplaced with nitrogen gas, vinyl chloride (67 g) was injected. Then,2,2′-azobis(2-amidinopropane) dihydrochloride (3.6 g) was added and thereaction was conducted at 60° C. for 5 hours to give an aqueousdispersion of a polymer.

Comparative Preparative Example 1

Into a 1 L autoclave, CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(CH₃)═CH₂ (n=2.0)(184 g), stearyl acrylate (23.1 g), glycerol monomethacrylate (4.3 g),glycidyl methacrylate (1.4 g), Siloxane 1 (aminomercapto silicone) (28.4g), pure water (500 g), tripropylene glycol (79.4 g), alkyl trimethylammonium chloride (3.7 g), sorbitan monopalmitate (4.5 g),polyoxyethylene oleyl ether (4.5 g) and polyoxyethylene lauryl ether(18.0 g) were charged and emulsified by ultrasonic wave at 60° C. for 15minutes with stirring. After the atmosphere of the autoclave wasreplaced with nitrogen gas, vinyl chloride (67 g) was injected. Then,2,2′-azobis(2-amidinopropane) dihydrochloride (3.6 g) was added and thereaction was conducted at 60° C. for 5 hours to give an aqueousdispersion of a polymer.

Comparative Preparative Example 2

Into a 1 L autoclave, CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(CH₃)═CH₂ (n=2.0)(184 g), stearyl acrylate (23.1 g), glycerol monomethacrylate (4.3 g),glycidyl methacrylate (1.4 g), pure water (500 g), tripropylene glycol(79.4 g), alkyl trimethyl ammonium chloride (3.7 g), sorbitanmonopalmitate (4.5 g), polyoxyethylene oleyl ether (4.5 g) andpolyoxyethylene lauryl ether (18.0 g) were charged and emulsified byultrasonic wave at 60° C. for 15 minutes with stirring. After theatmosphere of the autoclave was replaced with nitrogen gas, vinylchloride (67 g) was injected. Then, 2,2′-azobis(2-amidinopropane)dihydrochloride (3.6 g) was added and the reaction was conducted at 60°C. for 5 hours to give an aqueous dispersion of a polymer.

Comparative Preparative Example 3

Into a 1 L autoclave, CF₃CF₂—(CF₂CP₂)_(n)—CH₂CH₂OCOC(CH₃)═CH₂ (n=2.0)(184 g), stearyl acrylate (23.1 g), glycerol monomethacrylate (4.3 g),glycidyl methacrylate (1.4 g), pure water (500 g), tripropylene glycol(79.4 g), polyoxyethylene lauryl ether (18.0 g) and polyoxyethyleneisotridecyl ether (7.7 g) were charged and emulsified by ultrasonic waveat 60° C. for 15 minutes with stirring. After the atmosphere of theautoclave was replaced with nitrogen gas, vinyl chloride (67 g) wasinjected. Then, 2,2′-azobis(2-amidinopropane) dihydrochloride (3.6 g)was added and the reaction was conducted at 60° C. for 5 hours to givean aqueous dispersion of a polymer.

Comparative Preparative Example 4

Into a 1 L autoclave, CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(CH₃)═CH₂ (n=3.2)(204 g), stearyl acrylate (25.6 g), N-methylol acrylamide (6.4 g),3-chloro-2-hydroxypropyl methacrylate (1.5 g), pure water (486 g),tripropylene glycol (88 g), alkyl trimethyl ammonium chloride (3.4 g),sorbitan monopalmitate (4.6 g), polyoxyethylene oleyl ether (4.9 g) andpolyoxyethylene lauryl ether (20.0 g) were charged and emulsified byultrasonic wave at 60° C. for 15 minutes with stirring. After theatmosphere of the autoclave was replaced with nitrogen gas, vinylchloride (67 g) was injected. Then, 2,2′-azobis(2-amidinopropane)dihydrochloride (3.6 g) was added and the reaction was conducted at 60°C. for 5 hours to give an aqueous dispersion of a polymer.

Comparative Preparative Example 5

Into a 1 L autoclave, CF₃CF₂—(CF₂CF₂)_(n)—CH₂CH₂OCOC(CH₃)═CH₂ (n=3.2)(204 g), stearyl acrylate (25.6 g), N-methylol acrylamide (6.4 g),3-chloro-2-hydroxypropyl methacrylate (1.5 g), pure water (486 g),tripropylene glycol (88 g), sorbitan monopalmitate (4.6 g),polyoxyethylene oleyl ether (4.9 g) and polyoxyethylene lauryl ether(20.0 g) were charged and emulsified by ultrasonic wave at 60° C. for 15minutes with stirring. After the atmosphere of the autoclave wasreplaced with nitrogen gas, vinyl chloride (67 g) was injected. Then,2,2′-azobis(2-amidinopropane) dihydrochloride (3.6 g) was added and thereaction was conducted at 60° C. for 5 hours to give an aqueousdispersion of a polymer.

Examples 1 and 2

The aqueous dispersion (4.8 g) prepared by Preparative Examples 1 and 2was diluted with pure water to prepare a test liquid (100 g). One sheetof a nylon test fabric (510 mm×205 mm) was immersed in this test liquid,was passed through a mangle, and treated in a pin tenter at 160° C. for2 minutes. Then the test fabric was cut to give three thirds (each ofwhich has a size of 170 mm×205 mm). Three thirds of fabric was used fornon-washing, washing ten times and washing twenty times, respectively.The fabrics were subjected to the shower water-repellency test, thewater-repellency test and the oil repellency test. The same procedure asin the above manner was repeated for one sheet of a PET test fabric (510mm×205 mm) and one sheet of cotton test fabric (510 mm×205 mm). Theresults are shown in Table B.

Comparative Examples 1 to 5

The aqueous dispersion prepared by each of Comparative PreparativeExamples 1 to 5 was processed as in Example 1 and then the showerwater-repellency test, the water-repellency test and the oil repellencytest were conducted. The results are shown in Table B.

TABLE B Com. Com. Ex. 1 Ex. 2 Ex. 1 Ex. 2 Com. Com. Pre. Pre. Pre. Pre.Ex. 1 Ex. 2 Ex. 1 Ex. 2 WR Nylon HL0 100 100 100 100 (Spray) HL10 100 9080 80 HL20 90 80 80 80 Polyester HL0 100 100 100 100 HL10 100 100 90 90HL20 100 90 90 90 Cotton HL0 100 100 100 100 HL10 70 70 50 50 HL20 50 5050 50 OR Nylon HL0 6 6 5 5 HL10 5 5 4 4 HL20 5 4 4 4 Polyester HL0 7 7 66 HL10 7 6 6 6 HL20 6 6 5 5 Cotton HL0 6 6 5 5 HL10 5 4 4 4 HL20 4 2 2 2IPA/ Nylon HL0 6 6 6 6 Warter HL10 7 6 7 7 HL20 6 6 7 7 Polyester HL0 1010 9 9 HL10 10 9 8 8 HL20 10 9 7 7 Cotton HL0 6 6 5 5 HL10 6 5 5 5 HL204 4 2 2 Com. Com. Com. Ex. 3 Ex. 4 Ex. 5 Com. Pre. Com. Pre. Com. Pre.Ex. 3 Ex. 4 Ex. 5 WR Nylon HL0 100 100 100 (Spray) HL10 80 100 100 HL2080 90 90 Polyester HL0 100 100 100 HL10 90 100 100 HL20 90 100 100Cotton HL0 80 100 80 HL10 50 70 50 HL20 50 50 50 OR Nylon HL0 5 6 6 HL104 5 6 HL20 4 5 6 Polyester HL0 6 6 6 HL10 6 6 7 HL20 5 6 6 Cotton HL0 56 4 HL10 4 5 3 HL20 2 4 1 IPA/ Nylon HL0 6 7 7 Waiter HL10 7 7 7 HL20 77 7 Polyester HL0 9 8 8 HL10 8 10 10 HL20 7 8 9 Cotton HL0 5 5 3 HL10 54 2 HL20 2 3 1

1. An aqueous dispersion which comprises: (I) a fluorine-containingpolymer comprising repeating units derived from: (A) a monomer whichcomprises; (a) a fluorine-containing monomer of the formula:CH₂═C(X)COOYRf, wherein X is a hydrogen atom, a monovalent organicgroup, or a halogen atom, Y is a direct bond or a divalent organicgroup, and Rf is a fluoroalkyl group having 1 to 21 carbon atoms,wherein the monomer is polymerized in the presence of: (B) a functionalorganopolysiloxane selected from the group consisting of a mercaptofunctional organopolysiloxane, a vinyl functional organopolysiloxane anda (meth)acrylamide functional organopolysiloxane, and (II) water; and(III) an emulsifier consisting of a nonionic surfactant.
 2. The aqueousdispersion according to claim 1 wherein the fluorine-containing monomer(a) is a compound of the formula:CH₂═C(—X)—C(═O)—O—Y—Rf  (I) wherein X is a hydrogen atom, a linear orbranched alkyl group having 1 to 21 carbon atoms, a halogen atom, acyano group, a linear or branched fluoroalkyl group having 1 to 21carbon atoms, a substituted or unsubstituted benzyl group, a substitutedor unsubstituted phenyl group, or a CFX¹X² group, wherein X¹ and X² is ahydrogen atom or a halogen atom, Y is a direct bond, an aliphatic grouphaving 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having6 to 10 carbon atoms, a —CH₂CH₂N(R¹)SO₂— group, wherein R¹ is an alkylgroup having 1 to 4 carbon atoms, or a —CH₂CH(OY¹)CH₂— group, wherein Y¹is a hydrogen atom or an acetyl group, and Rf is a linear or branchedfluoroalkyl group having 1 to 21 carbon atoms.
 3. The aqueous dispersionaccording to claim 1 wherein the functional organopolysiloxane (B) is anamino-mercapto functional organopolysiloxane comprising siloxy unitshaving the average formula:(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(S)SiO)_(c) wherein a is 0-4000, b is1-1000, c is 1-1000, R is independently a monovalent organic group,R^(N) is a monovalent amino functional organic group, and R^(S) is amonovalent mercapto functional organic group.
 4. The aqueous dispersionaccording to claim 3 wherein the amino-mercapto functionalorganopolysiloxane has the average formula:

where a is 0-4000, b is 1-1000, c is 1-1000, and R′ is independently H,an alkyl group having 1 to 40 carbon atoms, or Me₃Si.
 5. The aqueousdispersion according to claim 1 wherein the functionalorganopolysiloxane (B) is a vinylamino functional organopolysiloxanecomprising siloxy units having the average formula:(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(V)SiO)_(c) wherein a is 0-4000, b is1-1000, c is 1-1000, R is independently a monovalent organic group,R^(N) is a monovalent amino functional organic group, and R^(V) is avinyl functional organic group.
 6. The aqueous dispersion according toclaim 5 wherein the vinylamino functional organopolysiloxane has theaverage formula:

where a is 0-4000, b is 1-1000, c is 1-1000, and R′ is independently H,an alkyl group having 1 to 40 carbon atoms, or Me₃Si.
 7. The aqueousdispersion according to claim 1 wherein the functionalorganopolysiloxane (B) is a (meth)acrylamide-amino functionalorganopolysiloxane comprising siloxy units having the average formula:(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(A)SiO)_(c) wherein a is 0-4000, b is1-1000, c is 1-1000, R is independently a monovalent organic group,R^(N) is a monovalent amino functional organic group, and R^(A) is a(meth)acrylamide functional organic group.
 8. The aqueous dispersionaccording to claim 1, wherein the monomer (A) further comprises: (b) afluorine-free monomer, and (c) optionally present, a crosslinkablemonomer, in addition to (a) the fluorine-containing monomer.
 9. Theaqueous dispersion according to claim 8, wherein the fluorine-freemonomer (b) is acrylates of the general formula:CH₂═CA¹COOA² wherein A¹ is a hydrogen atom, a methyl group or a halogenatom other than a fluorine atom, and A² is a hydrocarbon group having 1to 30 carbon atoms.
 10. The aqueous dispersion according to claim 8,wherein the crosslinkable monomer (c) is a monomer having at least tworeactive groups, a monomer having least two carbon-carbon double bonds,or a monomer having at least one carbon-carbon double bond and at leastone reactive group.
 11. The aqueous dispersion according to claim 8,wherein the crosslinkable monomer (c) is fluorine-free.
 12. The aqueousdispersion according to claim 1 wherein X is chlorine.
 13. The aqueousdispersion according to claim 1 wherein the dispersion further comprisesa compatibilizing agent selected from the group consisting of awater-soluble organic solvent and a low-molecular weight monomer.
 14. Amethod of producing an aqueous dispersion of a fluorine-containingpolymer comprising polymerizing: (A) a monomer which comprises; (a) afluorine-containing monomer of the formula:CH₂═C(X)COOYRf, wherein X is a hydrogen atom, a monovalent organicgroup, or a halogen atom, Y is a direct bond or a divalent organicgroup, and Rf is a fluoroalkyl group having 1 to 21 carbon atoms, in thepresence of; (B) a functional organopolysiloxane selected from the groupconsisting of a mercapto functional organopolysiloxane, a vinylfunctional organopolysiloxane and a (meth)acrylamide functionalorganopolysiloxane, and (III) an emulsifier consisting of a nonionicsurfactant in (II) water.
 15. The method according to claim 14 whereinthe fluorine-containing monomer is a compound of the formula:CH₂═C(—X)—C(═O)—O—Y—Rf  (I) wherein X is a hydrogen atom, a linear orbranched alkyl group having 1 to 21 carbon atoms, a halogen atom, acyano group, a linear or branched fluoroalkyl group having 1 to 21carbon atoms, a substituted or unsubstituted benzyl group, a substitutedor unsubstituted phenyl group, or a CFX¹X² group, wherein X¹ and X² is ahydrogen atom or a halogen atom, Y is a direct bond, an aliphatic grouphaving 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having6 to 10 carbon atoms, a —CH₂CH₂N(R¹)SO₂— group, wherein R¹ is an alkylgroup having 1 to 4 carbon atoms, or a —CH₂CH(OY¹)OH₂— group, wherein Y¹is a hydrogen atom or an acetyl group, and Rf is a linear or branchedfluoroalkyl group having 1 to 21 carbon atoms.
 16. The method accordingto claim 14 wherein the mercapto functional organopolysiloxane (B) is amercapto functional organopolysiloxane comprising siloxy units havingthe average formula:(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(S)SiO)_(c) wherein a is 0-4000, b is1-1000, c is 1-1000, R is independently a monovalent organic group,R^(N) is a monovalent amino functional organic group, and R^(S) is amonovalent mercapto functional organic group.
 17. The method accordingto claim 16 wherein the mercapto functional organopolysiloxane has theaverage formula:

where a is 0-4000, b is 1-1000, c is 1-1000, and R′ is independently H,an alkyl group having 1 to 40 carbon atoms, or Me₃Si.
 18. The methodaccording to claim 14 wherein the vinyl functional organopolysiloxane(B) is a vinylamino functional organopolysiloxane comprising siloxyunits having the average formula:(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(V)SiO)_(c) wherein a is 0-4000, b is1-1000, c is 1-1000, R is independently a monovalent organic group,R^(N) is a monovalent amino functional organic group, and R^(V) is avinyl functional organic group.
 19. The method according to claim 18wherein the vinylamino functional organopolysiloxane has the averageformula:

where a is 0-4000, b is 1-1000, c is 1-1000, and R′ is independently H,an alkyl group having 1 to 40 carbon atoms, or Me₃Si.
 20. The methodaccording to claim 14 wherein the functional organopolysiloxane (B) is a(meth)acrylamide functional organopolysiloxane comprising siloxy unitshaving the average formula:(R₂SiO)_(a)(RR^(N)SiO)_(b)(RR^(A)SiO)_(c) wherein a is 0-4000, b is1-1000, c is 1-1000, R is independently a monovalent organic group,R^(N) is a monovalent amino functional organic group, and R^(A) is a(meth)acrylamide functional organic group.
 21. The method according toclaim 14, wherein the monomer (A) further comprises: (b) a fluorine-freemonomer, and (c) optionally present, a crosslinkable monomer, Inaddition to (a) the fluorine-containing monomer.
 22. The methodaccording to claim 21, wherein the fluorine-free monomer (b) isacrylates of the general formula:CH₂═CA¹COOA² wherein A¹ is a hydrogen atom, a methyl group or a halogenatom other than a fluorine atom, and A² is a hydrocarbon group having 1to 30 carbon atoms.
 23. The method according to claim 21, wherein thecrosslinkable monomer (c) is a monomer having at least two reactivegroups, a monomer having least two carbon-carbon double bonds, or amonomer having at least one carbon-carbon double bond and at least onereactive group.
 24. The method according to claim 21, wherein thecrosslinkable monomer (c) is fluorine-free.
 25. The method according toclaim 14 wherein X is chlorine.
 26. The method according to claim 14wherein 5 to 99.9 weight % of the monomer (A), and 0.1 to 95 weight % ofthe functional organopolysiloxane (B), are used in the method providingthat sum of (A) and (B) equals 100%.
 27. The aqueous dispersion preparedaccording the method of claim
 14. 28. A surface treatment agentcomprising the aqueous dispersion according to claim
 1. 29. The surfacetreatment agent according to claim 28, which further comprises a liquidmedium.
 30. A method of treating a substrate with the surface treatmentagent according to claim
 28. 31. A textile which is treated with thesurface treatment agent according to claim 28.